1(nitro phenyl)-nitro or halo-mercaptobenzothiazoles



Patented Jan. 29, 1935 Q 5-:

UNI-TED;STATES? nmrno PHENYL) NITRO onjnAno-amn CAPTOBENZOTHIAZOLES Jan Teppema, Akron, Ohio, assignor to wingfoot Corporation,-Wilmington, Del., a corporatlon of Delaware No Drawing. Application-February 6, 1929,

- Serial No. 338,050

14 Claims. (01.260-{4411 v My invention relates to a new class of chemical compounds; more particularly, to certain.

mercaptothiazole derivatives not heretofore known to the art. One of the objects of my in-- vention is to provide a new class of compounds paring compounds of the kindabove mentioned.

My invention involves, among other things,

the discovery of a new class of nitro benzene derivatives of the thiazoles and a commercial method of preparing them. The compound 2,4 di-nitro phenyl mercaptobenzothiazole,

is a particular example of such material. Inits preparation, the sodium salt of mercaptobenzoemployedisrelatively unimportant, butv a sufficient' amount should be used to insure complete solution. Reaction takes place between the mercaptobenzothiazole and the 2,4 di-nitro chlor benzene upon heating the solution to the boiling point at atmospheric pressures. Upon allowing the solution to stand and cool, the reaction product (2,4 di-nitro phenyl mercaptobenzothiazole) is precipitated as a crystalline material having, when pure, a melting point of 162 C.

Analogous reactionproducts may be prepared by the method employed in the preparation of the compound just discussed. A few of the materials which may be so prepared are 2,4 di-nitro phenyl 4-nitro mercaptobenzothiazole having the formula and having a melting point of 185 to 187 0.; 2.4

di-nitro phenyl 5-chlor mercaptobenzothiazole having the formula which has a inennig point of 165I c.; 2,4 di-ni- OFFICE j 1' trophenyl 4 -nitro Y 5-chlor benzothiazole having 10 the formula v p I N- N02 Nor V the melting point of which is 172 C. Obviously, alkyl substituted mercaptobenzothiazoles may be employed in lieu of the chlorand nitro-substituted thiazoles of the above formulae. Examples of such thiazoles are the methyl 'anddi- I methyl'substituted mercaptobenzothiazole prepared from toluidine and xylidene by causing themito react, under heat and pressure in an autoclave, with sulfur and carbon bisulfide.

The mono nitro chlor benzenes likewise will reactiwith the sodium salt of mercaptobenzothiazole and with the sodium salts of most, if not all-,

.. .of the ordinary derivatives thereof. Thefor'mula of the 2-nitro chlor benzene derivatives of mercaptobenzothiazole (2-nitro-phenyl mercaptobenzothiazole) may be represented by the following formula:

This compound melts at to 112 C. other examples are the 2-nitro phenyl chlor mercaptobenzothiazoles, the 2-nitro phenyl nitro mercaptobenzothiazoles, nitro phenyl chlor the 2-nitro mercaptobenzothiazoles, and the 2-nitro phenyl methyl mercaptobenzothiazoles. The reaction between the mercaptobenzotliiazole compounds and the mono nitro chlor benzenes is usually somewhat slower than that between the corresponding thiazoles and 2,4 di-nitro chlor benzene. For that reason, it is preferable to conduct the reaction in an autoclave under heat and pressure. A temperature of approximately to 200 C. will in general be found sufficient to produce satisfactory results.

Still other materials may be prepared by emtaining methyl, chlor, sulfonic, nitro or other groups in positions 3 or 5.

Mono-nitro phenyl derivatives of mercaptothiazoles, whether or not containing methyl, chlor, sulfonic or other substituent groups in positions 3 or 5, may as a rule be purified by recrystallization from alcohol; in :which they mare iusuallyk readily soluble." On the-other'hand,'the2,-4 dinitro compounds; e. g., 2, 4 di-nitro phenyl mercaptobenzothiazole, are only sparingly soluble in that material. Accordingly, it is, preferable totem? ploy aniline or toluene as solventsiii theilixbiliie fication. Other solvents may, however, be used if desired.

All of the reactions described-'take= plaoewith comparative readiness and no expensive or complicated apparatus is necessary in connectiontherewith. The compounds in question are-.ob1-; tained in large and, in many cases, substantially, quantitative yields. alsocomparatively pure and "may bereduced topractical purity by the simple processv of, recrys- I tallization from any of the solvents above mentioned. However, for many purposes the products are obtained in suflicient purity? from the mother liquor and further purification is unnecessary.

Although Lhavedescribed in detail only the preferred l embodiments of :the, invention, it be apparent to those skilled in the art thatit is not limited thereto, but that various modifications may be made therein without departing from the spirit of the invention or from the. scope of the appended claims. It is intended that the patent shall cover; by suitable expression in the appended claims, whatever, features of patentable'novelty reside in the invention.

What I claim is: i 1

1. A-nitro phenyl chlorzbenzothiazyl sulphide.

2. A di-nitro phenylfnitro benzothia'zyl-sul-L phide. I

3. A di-nitro phenyl nitro chlor 'benzothiazylz sulphide.

4. A nitro. phenyl nitro benzothiazyl-sulphide 5. A nitro phenyl-nitro chlorbenzothiazylsul' v phide.

6'. A. dinitro phenylchlor benzothiazyl;:"sul?-;:.

phide;

7. A' compound having the formula:

R c-s-R:

wherein R and R are nitro substituted hydrocarbons of the benzene series;

The reaction products are 8. A compound having the formula series.

10. A compound having the formula wherein and- R are" respectively chlor-, and

nitro-;substitutedihydrocarbons of the benzene series. Q

lli'A compound havingth'e ior'mula whereimR and Rf arerespectivelychlor-and dinitro-' substitutedhydrocarbons of the benzene series; I

12. A compound. having the formula wherein R and Rf are respectivelymitro chlorand nitrosubstituted hydrocarbons of the benzene series.

13. A compound having the formula wherein R and R are respectively nitro chlorand dinitrosubstituted-hydrocarbons of the benzene series. 7

14. Thiazyl compounds of. the .,group consisting of. the. nitro phenyl 'nitr'o benzo thi'azyl. sulphides and. the nitro phenyl halobenzothiazyl sulphides. V JAN 'I'EBPEMA. 

